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EP0046342B1 - Detergent compositions and processes of making thereof - Google Patents

Detergent compositions and processes of making thereof Download PDF

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Publication number
EP0046342B1
EP0046342B1 EP81303363A EP81303363A EP0046342B1 EP 0046342 B1 EP0046342 B1 EP 0046342B1 EP 81303363 A EP81303363 A EP 81303363A EP 81303363 A EP81303363 A EP 81303363A EP 0046342 B1 EP0046342 B1 EP 0046342B1
Authority
EP
European Patent Office
Prior art keywords
dispersing agent
siloxane
oxyalkylene
nonionic surfactant
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81303363A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0046342A1 (en
Inventor
Shafiq Dhanani
Ronald Macdonald
James Spence Clunie
Maxim Courtney Brooks
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Ltd
Procter and Gamble Co
Original Assignee
Procter and Gamble Ltd
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Ltd, Procter and Gamble Co filed Critical Procter and Gamble Ltd
Priority to AT81303363T priority Critical patent/ATE11791T1/de
Publication of EP0046342A1 publication Critical patent/EP0046342A1/en
Application granted granted Critical
Publication of EP0046342B1 publication Critical patent/EP0046342B1/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones

Definitions

  • This invention relates to detergent compositions and to processes of making thereof.
  • it relates to heavy duty detergent compositions having controlled sudsing characteristics especially when used in automatic washing machines for washing clothes and the like.
  • Detergent compositions normally contain surfactants which tend to produce foam when agitated in aqueous solution. For many applications, especially in automatic washing and dishwashing machines, excess foam production is a serious problem and with many effective surfactants it is necessary to add foam suppressing or controlling agents in order to achieve acceptable sudsing characteristics.
  • foam controlling agents can in itself create new problems.
  • monostearyl acid phosphate which is one conventional controlling agent, is very effective and useful at low levels in product, but as the level of phosphate is increased to cope, for example, with increased surfactant, the material becomes incompletely soluble in the wash solution and precipitates out of solution onto utensil and machine surfaces leaving them coated with unsightly streaks and deposits.
  • silicones especially polydimethylsiloxane. These materials are known to be very useful in industrial applications where the silicone is added directly to an aqueous solution containing a surfactant. However, they have not lived up to their promise when incorporated into detergent compositions; frequently, for example, they become inactivated in the presence of other detergent ingredients and require some type of special protection as disclosed, for instance, in US-A-3,933,672. Also, in the case of granular compositions, addition of silicone foam-controllers can lead to problems of increased "wetting" of detergent substrate in an aqueous medium with. the result that the product has poor dispensing characteristics in washing machines and leaves gel-like residues on the inside of the product dispenser. In addition, silicone foam-controllers can have a deleterious effect on the surface-feel of fabrics washed therein, and can also adversely affect the cleaning characteristics of detergent compositions.
  • silicone-based foam-controller which requires no special protection to prevent inactivation in the presence of other detergent ingredients, is the so-called "self-emulsified" silicone class disclosed generally in GB-A- 1 ,533,61 0 and GB-A-1,554,736.
  • the preferred self-emulsified foam-controller disclosed therein are those containing emulsifiers having at least one polyoxyalkylene moiety incorporated into a basic polysiloxane structure. Mixtures of these emulsifiers with polydimethylsiloxanes are also generally disclosed, the mixtures containing at least 50% of emulsifier and from about 5% to 45% of polydimethylsiloxane liquid.
  • the "self-emulsified” silicone foam-controllers disclosed above successfully overcome the inactivation problem in the presence of other detergent ingredients, they are still found to suffer a number of drawbacks which limit their commercial and practical value.
  • the "self-emulsified” silicones are found to be relatively inefficient foam-controllers, in other words, one requires a relatively high level of the foam regulating material for satisfactory performance.
  • "self-emulsified” silicones are found to be relatively sensitive to the prevailing wash conditions (soil load, fabric/liquor ratio, wash temperature etc); in other words, “self-emulsified” silicones lack “robustness”.
  • the "self-emulsified” silicones tend to have a flocculating effect on silica dispersions and this can lead to a loss of suds suppression effectiveness after prolonged storage of the foam controller in a detergent composition.
  • the present invention thus provides a detergent composition having improved foam control characteristics, especially foam-controller efficiency, robustness and storage stability; it also provides a detergent composition having improved foam control without detriment to detergency performance or "feel" characteristics of fabrics washed therein; and it further provides a foam-controlled detergent composition having excellent dispensing characteristics in automatic washing machines.
  • the present invention provides a foam-controlled detergent composition
  • a foam-controlled detergent composition comprising from 1.5% to 100% by weight, preferably from 5% to 60% by weight of a mixture of:
  • nonionic surfactant is an ethoxylated nonionic surfactant having an average ethyleneoxy content of from 35% to 70%, especially from 47.5% to 67.5%, more especially from 50% to 62.5%.
  • a preferred class of nonionic surfactant is the condensation product of a C 8 to C 24 primary or secondary aliphatic alcohol with from 2 to 18 moles of ethylene oxide per mole of alcohol.
  • compositions of the invention suitably contain from 2% to 35%, preferably from 5% to 20% of nonionic surfactant and from 0.05% to 0.75%, preferably from 0.1% to 0.4% in total of polydimethylsiloxane foam-controller and siloxane-oxyalkylene dispersing agent.
  • the polydimethylsiloxane foam controller is dispersed in the nonionic surfactant in combination with particulate silica in a weight ratio of siloxane:silica of from 20:1 to 200:1, more preferably from 25:1 to 100:1. Addition of the silica is valuable for enhancing the foam-controlling effectiveness of the present compositions.
  • the storage stability of the resulting compositions is particularly sensitive to the ratio both of polydimethylsiloxane to silica and of polydimethylsiloxane to dispersant and control of both these parameters is therefore important for obtaining optimum performance.
  • a granular detergent composition comprising
  • a process for making the foam-controlled detergent compositions comprising the steps of forming a surfactant premix comprising at least part of the nonionic surfactant, the polydimethylsiloxane foam controller and siloxane-oxyalkylene dispersing agent and subjecting the premix in fluent foam to high shear mixing.
  • the premix is then preferably sprayed in fluent form onto a base powder composition comprising:-
  • the surfactant premix is prepared by first preparing a premix of alkoxylated nonionic surfactant and siloxane-oxyalkylene dispersing agent, admixing the polydimethylsiloxane foam controller and, where present, particulate silica with the surfactant/dispersing agent mixture, and thereafter subjecting the total mixture to high shear mixing.
  • alkoxylated nonionic surfactants can be used in the present compositions.
  • a typical listing of the classes and species of these surfactants is given in US-A-3,664,961.
  • Alkoxylated nonionic surfactants materials can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • the nonionic surfactants are ethoxylated surfactants.
  • ethoxylated nonionic surfactants suitable herein have an average ethyleneoxy content in the range from 35% to 70% and especially from 50% to 62.5% by weight of the surfactant.
  • nonionic surfactants include the condensation products of primary or secondary aliphatic alcohols having from 8 to 24 carbon atoms, in either straight chain or branched chain configuration, with from 2 to 18 moles of alkylene oxide per mole of alcohol.
  • the aliphatic alcohol comprises between 9 and 15 carbon atoms and is ethoxylated with between 2 and 9, desirably between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol.
  • Such nonionic surfactants are preferred from the point of view of providing good to excellent detergency performance on fatty and greasy soils, and in the presence of hardness sensitive anionic surfactants such as alkyl benzene sulfonates.
  • the preferred surfactants are prepared from primary alcohols which are either linear (such as those derived from natural fats or, prepared by the Ziegler process from ethylene, e.g. myristyl, cetyl, stearyl alcohols, or partly branched such as the Dobanols® and Neodols® which have about 25% 2-methyl branching (Dobanol@ and Neodol@ being Trade Names of Shell) or Synperonics@, which are understood to have about 40% to 50% 2-methyl branching (Synperonic@ is a Trade Name of I.C.I.), or the primary alcohols having more than 50% branched chain structure sold under the Trade Name of Lial by Liquichimica.
  • primary alcohols which are either linear (such as those derived from natural fats or, prepared by the Ziegler process from ethylene, e.g. myristyl, cetyl, stearyl alcohols, or partly branched such as the Dobanols® and Neodols® which have about
  • nonionic surfactants falling within the scope of the invention include Dobanol@ 45-4, Dobanol@ 45-7, Dobanol@ 45-9, Dobanol@ 91-3, Dobanol@ 91-6, Dobanol@ 91-8, Synperonic@ 6, Synperonic@ 9, the condensation products of coconut alcohol with an average of between 5 and 9 moles of ethylene oxide per mole of alcohol, the coconut alkyl portion having from 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow portion comprising essentially between 16 and 22 carbon atoms.
  • Secondary linear alkyl ethoxylates are also suitable in the present compositions, for example, those ethoxylates of the Tergitol® series having from 9 to 15 carbon atoms in the alkyl group and up to 11, especially from 3 to 9, ethoxy residues per molecule.
  • alkoxylated nonionic surfactants having an average HLB in the range from 9.5 to 13.5, especially 10 to 12.5.
  • Highly suitable nonionic surfactants of this type are ethoxylated primary C 9-15 alcohols having an average degree of ethoxylation from 2 to 9, more preferably from 3 to 8.
  • the polydimethylsiloxane foam controllers used herein are high molecular weight compounds having a molecular weight in the range from 200 to 200,000, and have a kinematic viscosity in the range from 20 to 2,000,000 mm 2 /s, preferably from 500 to 50,000 mm 2 /s, more preferably from 3,000 to about 30,000 mm 2 /s at 25°C.
  • the siloxane polymer is generally end-blocked either with trimethylsilyl or hydroxyl groups but other end-blocking groups are also suitable.
  • the polymer can be prepared by various techniques such as the hydrolysis and subsequent condensation of dimethyldihalosilanes, or by the cracking and subsequent condensation of dimethylcyclosiloxanes.
  • the polydimethylsiloxanes can also be present in combination with particulate silica.
  • Such combinations of silicone and silica can be prepared by affixing the silicone to the surface of silica for example by means of the catalytic reaction disclosed in US-A-3,235,509.
  • Foam regulating agents comprising mixtures of silicone and silica prepared in this manner preferably comprise silicone and silica in a silicone:silica ratio of from 20:1 to 200:1, preferably 25:1 to 100:1.
  • the silica can be chemically and/or physically bound to the silicone in an amount which is preferably 0.5% to 5% by weight, based on the silicone.
  • the particle size of the silica employed in such silica/silicone foam regulating agents should preferably be not more than 100 nm preferably from 10 nm to 20 nm, and the specific surface area of the silica should exceed 50 m 2 /g.
  • foam regulating agents comprising silicone and silica can be prepared by admixing a silicone fluid of the type herein disclosed with a hydrophobic silica having a particle size and surface area in the range disclosed above.
  • a hydrophobic silica which can be employed herein in combination with a silicone as the foam regulating agent.
  • a fumed silica can be reacted with a trialkyl chlorosilane (i.e., "silanated") to affix hydrophobic trialkylsilane groups on the surface of the silica.
  • fumed silica is contacted with trimethylchlorosilane.
  • a preferred foam regulating agent herein comprises a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from 10 nm to 20 nm and a specific surface area above 50 m 2 /g intimately admixed with a dimethyl silicone fluid having a molecular weight in the range of from 500 to 200,000, at a weight ratio of silicone to silanated silica of from 20:1 to 200:1, preferably from 20:1 to 100:1.
  • a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from 10 nm to 20 nm and a specific surface area above 50 m 2 /g intimately admixed with a dimethyl silicone fluid having a molecular weight in the range of from 500 to 200,000, at a weight ratio of silicone to silanated silica of from 20:1 to 200:1, preferably from 20:1 to 100:1.
  • foam regulating agent suitable herein comprises polydimethylsiloxane fluid, a silicone resin and silica.
  • the silicone "resins” used in such compositions can be any alkylated silicone resins, but are usually those prepared from methylsilanes. Silicone resins are commonly described as "three-dimensional” polymers arising from the hydrolysis of alkyl trichlorosilanes, whereas the silicone fluids are "two-dimensional" polymers prepared from the hydrolysis of dichlorosilanes.
  • the silica components of such compositions are the microporous materials such as the fumed silica aerogels and xerogels having the particle sizes and surface areas herein-above disclosed.
  • the mixed polydimethylsiloxane fluid/silicone resin/silica materials useful in the present compositions can be prepared in the manner disclosed in US-A-3,455,839. These mixed materials are commercially available from the Dow Corning Corporation. Preferred materials of this type comprise:
  • the siloxane-oxyalkylene dispersing agent suitable for use herein has the general formula I: wherein a is 0 or an integer from 1 to 3, R is an alkyl group containing from 1 to 30 carbon atoms, or a group of formula II: wherein R' is an alkylene group containing from 1 to 6 carbon atoms, b has a value of from 1 to 100, preferably from 10 to 30; and R" is a capping group which can be selected from hydrogen, alkyl, acyl, aryl, alkaryl, aralkyl or alkenyl groups containing up to 20 carbon atoms, sulfate, sulfonate, phosphate, carboxylate, phosphonate, borate or isocyanate groups, or mixtures thereof; Y is a group having the formula III:- wherein R is as defined above and c has a value from 1 to 200; and wherein at least one R group in the compound has the formula II.
  • Preferred dispersing agents of the above type are selected from compounds having the general formulae IV to VII. wherein R'" is a C 1-10 alkyl group, Me is methyl, G is the group of formula II, a has a value of 0 or 1, p has a value of at least 1, q has a value of 0 to 50 and r has a value of 1 to 50.
  • Preferred dispersants contain G groups in non-terminal positions and contain a mixture of oxyethylene and oxypropylene groups, particularly in about a 1:1 ratio. Highly preferred are dispersants of formula VII having p+r from 30 to 120 with the ratio p:r from 2:1 to 8:1.
  • compositions of the invention can be supplemented by all manner of detergent components.
  • a highly preferred additional component is from 1% to 15%, especially from 2% to 8% of organic surfactant selected from anionic, zwitterionic and ampholytic surfactants and mixtures thereof.
  • Suitable synthetic anionic surfactants are water-soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxyl ether sulfates, paraffin sulfonates, alpha-olefin sulfonates, alpha- sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2-acyloxy-alkane-1-sulfonate, and beta-alkyloxy alkane sulfonate.
  • a particularly suitable class of anionic detergents includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts or organic sulfuric reaction products having in their molecular structure an alkyl or alkaryl group containing from 8 to 22, especially from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term “alkyl” is the alkyl portion of acyl groups).
  • Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 ) carbon atoms produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from 9 to 15, especially 11 to 13, carbon atoms, in straight chain or branched chain configuration, e.g.
  • anionic detergent compounds herein include the sodium C 10 -C 18 alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain 8 to 12 carbon atoms.
  • Other useful anionic detergent compounds herein include the water-soluble salts or esters of ⁇ -sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 18, especially 12 to 16, carbon atoms in the alkyl group and from 1 to 12, especially 1 to 6, more especially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from 12 to 24, preferably 14 to 16, carbon atoms, especially those made by reaction with sulfur trioxide followed by neutralization under conditions such that any sulfones present are hydrolysed to the corresponding hydroxy alkane sulfonates; water-soluble salts of paraffin
  • alkane chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium or alkanolammonium cations; sodium is preferred. Magnesium and calcium are preferred cations under circumstances described by BE-A-843,636.
  • a preferred mixture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group or paraffin sulfonate having 14 to 18 carbon atoms and either an alkyl sulfate having 8 to 18, preferably 12 to 18, carbon atoms in the alkyl group, or an alkyl polyethoxy alcohol sulfate having 10 to 16 carbon atoms in the alkyl group and an average degree of ethoxylation of 1 to 6.
  • Suitable ampholytic surfactants are water-soluble derivatives of aliphatic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Suitable zwitterionic surfactants are water soluble derivatives of aliphatic quaternary ammonium phosphonium and sulfonium cationic compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.
  • composition of the invention can also contain from at least 5% of detergency builder, preferably from 20% to 80% thereof.
  • Suitable detergent builder salts useful herein can be of the polyvalent inorganic and polyvalent organic types, or mixtures thereof.
  • suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, polyphosphates, tripolyphosphates and bicarbonate.
  • Suitable organic alkaline detergency builder salts are:
  • Mixtures of organic and/or inorganic builders can be used herein.
  • One such mixture of builders is disclosed in CA-A-755,038, e.g. a ternary mixture of sodium tripolyphosphate, trisodiumnitrilo- triacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
  • a further class of builder salts is the insoluble alumino silicate type which functions by cation exchange to remove polyvalent mineral hardness and heavy metal ions from solution.
  • a preferred builder of this type has the formulation Na 2 (AlO 2 ) 2 (SiO 2 ) Y . xH 2 O wherein z and are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5 and x is an integer from 15 to 264.
  • Compositions incorporating builder salts of this type form the subject of GB-A-1,429,143, DE-A-2,433,485 and DE-A-2,525,778.
  • Another suitable component of the present compositions is a water-soluble magnesium salt which is added at levels in the range from 0.015% to 0.2%, preferably from 0.03% to 0.15% and more preferably from 0.05% to 0.12% by weight of the compositions (based on weight of magnesium).
  • Suitable magnesium salts include magnesium sulfate, magnesium sulfate heptahydrate, magnesium chloride, magnesium chloride hexahydrate, magnesium fluoride and magnesium acetate.
  • the magnesium salt is added to the compositions as part of the aqueous slurry crutcher mix and is then converted to dry granular form, for instance by spray drying.
  • the magnesium salt can provide additional low temperature stain removal benefits as described in EP-A-40038, published November 18, 1981.
  • Bleaching agents can also be incorporated in the compositions of the present invention, for example, sodium perborate tetrahydrate and monohydrate, sodium percarbonate, chlorinated trisodium phosphate and the sodium and potassium salts of dichloroisocyanuric acid.
  • the bleaching agent can also be used in admixture with an aminopolyphosphonic acid, or salt thereof, such as ethylenediamine tetra(methylenephosphonic acid) or diethylenetriamine penta(methylenephosphonic acid), a preferred system of this kind also being disclosed in EP-A-40038 published November 18, 1981.
  • Soil-suspending agents at 0.1 % to 10% by weight such as water-soluble salts of carboxymethylcellulose, carboxyhydroxymethyl cellulose, polyethylene glycols having a molecular weight of 400 to 10,000 and copolymers of maleic anhydride with methyl vinyl ether, ethylene or acrylic acid, are common components of the present invention. Dyes, pigment, optical brighteners, and perfumes can be added in varying amounts as desired.
  • Enzymes suitable for use herein include those discussed in US-A-3,519,570 and US-A-3,533,139.
  • Anionic fluorescent brightening agents are well-known materials, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2:2' disulphonate, disodium 4,4'- bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'-dilsulphonate, disodium 4,4'-bis-(2,4-di- anilino-s-triazin-6-ylamino)stilbene-2:2'-di-sulphonate, disodium 4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'-disulphonate, disodium 4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2'-
  • alkali metal, or alkaline earth metal, silicate can also be present.
  • the alkali metal silicate is preferably from 3% to 8%.
  • Suitable silicate solids have a molar ratio of SiO 2 /alkali metal 2 O in the range from 1.0 to 3.3, more preferably from 1.5 to 2.0.
  • foam regulating materials can also be incorporated in the compositions of the invention if desired.
  • Suitable materials include the microcrystalline waxes disclosed in GB-A-1,492,938 and C 18-22 fatty acids or soaps thereof.
  • compositions include organic peroxyacid precursors such as methyl o-acetoxy benzoate, sodium p-acetoxy benzene sulfonate, bisphenol A diacetate, tetraacetyl ethylene diamine, tetraacetyl hexamethylene diamine and tetraacetyl methylene diamine.
  • a filler such as an alkali metal sulfate is also a desirable additive, and can be present at levels from 1 % to 90%, preferably from 5% to 30% by weight of the compositions.
  • the polydimethylsiloxane foam controller is intimately mixed, preferably by high shear mixing, with at least a part of the nonionic surfactant and with siloxane- oxyalkylene dispersing agent in a fluent (if necessary molten) nonionic surfactant phase and the liquid - mixture is sprayed, coated or adsorbed onto a base powder granule containing some or all of the remaining ingredients of the composition.
  • the following granular detergent compositions are prepared by mixing all ingredients, apart from nonionic surfactant, bleach, DC544@, DC200@ and enzyme, in a crutcher as an aqueous slurry, spray-drying the slurry at high temperature in a spray-drying tower to form a base granule, admixing bleach and enzyme with the spray-dried detergent base powder, high shear mixing the nonionic surfactant with DC544@ and DC200@ and spraying the mixture onto the granular base powder.
  • the above compositions display superior foam regulation characteristics after prolonged storage under warm, humid conditions; they provide excellent detergency performance without detriment to the "handle” of the fabrics washed therein; and they also provide excellent product dispensing characteristics in drum-type automatic washing machines.
  • the following granular detergent compositions are prepared by mixing all ingredients, apart from nonionic surfactant, bleach, DC 198@, DC 200@, silicone, silica and enzyme, in a crutcher as an aqueous slurry, spray-drying the slurry at high temperature in a spray-drying tower to form a base granule, admixing bleach and enzyme with the spray-dried detergent base powder, forming a first mix containing the nonionic surfactant and DC 198®, forming a second mix of DC 200® and silica or silicone/silica, combining the two mixes, subjecting the combined mixture to high shear mixing, and finally spraying the mixture onto the granular base powder.
  • the above compositions display superior foam regulation characteristics after prolonged storage under warm, humid conditions; they provide excellent detergency performance without detriment to the "handle” of the fabrics washed therein; and they also provide excellent product dispensing characteristics in drum-type automatic washing machines.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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EP81303363A 1980-07-28 1981-07-23 Detergent compositions and processes of making thereof Expired EP0046342B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81303363T ATE11791T1 (de) 1980-07-28 1981-07-23 Detergenszusammensetzungen und verfahren zu ihrer herstellung.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8024570 1980-07-28
GB8024570 1980-07-28
GB8115314 1981-05-19
GB8115314 1981-05-19

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EP0046342A1 EP0046342A1 (en) 1982-02-24
EP0046342B1 true EP0046342B1 (en) 1985-02-13

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US (1) US4400288A (el)
EP (1) EP0046342B1 (el)
CA (1) CA1185870A (el)
DE (1) DE3168893D1 (el)
ES (1) ES504304A0 (el)
GR (1) GR75649B (el)
MX (1) MX153402A (el)

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US7592296B2 (en) 2004-08-03 2009-09-22 Johnsondiversey, Inc. Conveyor track or container lubricant compositions

Families Citing this family (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3373918D1 (en) * 1982-04-13 1987-11-05 Procter & Gamble Foam-controlling detergent additive compositions and use thereof in detergent compositions
GB8323131D0 (en) * 1983-08-27 1983-09-28 Procter & Gamble Ltd Detergent compositions
GB8401875D0 (en) * 1984-01-25 1984-02-29 Procter & Gamble Liquid detergent compositions
GB8413802D0 (en) 1984-05-30 1984-07-04 Procter & Gamble Detergent with suds control
US4652392A (en) * 1985-07-30 1987-03-24 The Procter & Gamble Company Controlled sudsing detergent compositions
US4818421A (en) * 1987-09-17 1989-04-04 Colgate-Palmolive Co. Fabric softening detergent composition and article comprising such composition
US4978471A (en) * 1988-08-04 1990-12-18 Dow Corning Corporation Dispersible silicone wash and rinse cycle antifoam formulations
US4983316A (en) * 1988-08-04 1991-01-08 Dow Corning Corporation Dispersible silicone antifoam formulations
CA1340040C (en) * 1988-08-26 1998-09-15 Dow Corning Corporation Method of enhancing fabric rewettability
US4846982A (en) * 1988-09-30 1989-07-11 Dow Corning Corporation Particulate fabric laundering composition
GB8823875D0 (en) * 1988-10-12 1988-11-16 Dow Corning Sa Softening compositions
MY118065A (en) * 1989-10-26 2004-08-30 Toshiba Silicone Cleaning compositions
US5503681A (en) * 1990-03-16 1996-04-02 Kabushiki Kaisha Toshiba Method of cleaning an object
US5593507A (en) * 1990-08-22 1997-01-14 Kabushiki Kaisha Toshiba Cleaning method and cleaning apparatus
ES2091450T3 (es) * 1992-03-06 1996-11-01 Procter & Gamble Composiciones detergentes controladoras de espuma.
US5686404A (en) * 1992-03-06 1997-11-11 The Procter & Gamble Company Suds controlling compositions
US5830841A (en) * 1992-06-06 1998-11-03 The Procter & Gamble Company Suds controlling compositions comprising silicone and silica
US5643862A (en) * 1992-06-06 1997-07-01 The Procter & Gamble Company Stable foam-controlled liquid detergent compositions
DE69214275T2 (de) * 1992-06-06 1997-04-17 The Procter & Gamble Co., Cincinnati, Ohio Zusammensetzungen zur Schaumbegrenzung
WO1995002665A1 (en) * 1993-07-12 1995-01-26 The Procter & Gamble Company Granular detergent composition comprising a surfactant and antifoaming component
US5804544A (en) * 1993-07-12 1998-09-08 Procter & Gamble Company Granular detergent composition comprising a surfactant and antifoaming component
GB9315671D0 (en) * 1993-07-29 1993-09-15 Dow Corning Sa Foam control agents and their use
US5589449A (en) * 1993-07-29 1996-12-31 Dow Corning S.A. Particulate foam control agents
GB9315675D0 (en) * 1993-07-29 1993-09-15 Dow Corning Sa Particulate foam control agents
US5968872A (en) * 1993-10-13 1999-10-19 Witco Corporation Foam control agents for silicone surfactants in agriculture
US5538667A (en) * 1993-10-28 1996-07-23 Whitehill Oral Technologies, Inc. Ultramulsions
EP0666301A1 (en) * 1994-02-04 1995-08-09 The Procter & Gamble Company Stable liquid detergent compositions
US5968889A (en) * 1994-03-30 1999-10-19 The Procter & Gamble Company Detergent compositions comprising a synergistic antifoaming combination
US5856282A (en) * 1994-12-22 1999-01-05 The Procter & Gamble Company Silicone compositions
GB9426236D0 (en) * 1994-12-24 1995-02-22 Dow Corning Sa Particulate foam control agents and their use
CA2230310A1 (en) * 1995-09-04 1997-03-13 Unilever Plc Detergent compositions and process for preparing them
US6169063B1 (en) * 1997-04-04 2001-01-02 The Procter & Gamble Company Low sudsing granular detergent composition containing optimally selected levels of a foam control agent and enzymes
US6403548B1 (en) 1998-10-27 2002-06-11 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Wrinkle reduction laundry product compositions
US6426328B2 (en) 1998-10-27 2002-07-30 Unilever Home & Personal Care, Usa Division Of Conopco Inc. Wrinkle reduction laundry product compositions
US6376456B1 (en) 1998-10-27 2002-04-23 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Wrinkle reduction laundry product compositions
US5972867A (en) * 1998-12-02 1999-10-26 Cogate Palmolive Company High foaming, grease cutting light duty liquid detergent
CA2352097A1 (en) * 1998-12-02 2000-06-08 Leonard Zyzyck High foaming, grease cutting light duty liquid detergent
US6221922B1 (en) * 1999-03-23 2001-04-24 Crompton Corporation Foam control agents for silicone surfactants
ES2251454T3 (es) * 2001-03-26 2006-05-01 THE PROCTER & GAMBLE COMPANY Proceso para limpiar superficies duras con una composicion limpiadora liquida que comprende un blanqueador.
ES2247321T3 (es) * 2001-04-30 2006-03-01 Unilever N.V. Composiciones de cuidado de tejidos.
EP1879972A4 (en) * 2005-05-09 2008-10-15 Ndsu Res Foundation ANTIFOULIN MATERIALS WITH POLYAMINE NETWORK POLYSILOXANES
US8372384B2 (en) * 2007-01-08 2013-02-12 Ndsu Research Foundation Quaternary ammonium functionalized cross-linked polyalkylsiloxanes with anti-fouling activity
US8709394B2 (en) * 2007-09-28 2014-04-29 Ndsu Research Foundation Antimicrobial polysiloxane materials containing metal species
US20100004202A1 (en) * 2008-02-15 2010-01-07 Ndsu Research Foundation Quaternary ammonium-functionalized-POSS compounds
EP2324103A4 (en) * 2008-08-14 2012-05-30 Melaleuca Inc ULTRACONCENTRATED LIQUID LAUNDRY DETERGENT
MX351856B (es) 2010-12-16 2017-10-31 Akzo Nobel Chemicals Int Bv Composicion de desengrasado de bajo picado.
EP2720988A4 (en) * 2011-06-17 2015-03-04 Kemira Oyj POWDER DISPOSAL COMPOSITIONS AND METHOD FOR REDUCING THE INTRUSION OF GAS IN LIQUIDS
KR102348559B1 (ko) * 2019-12-23 2022-01-06 현대오일뱅크 주식회사 하이드로카본 폼 저감 및 실리콘 넘김 저감을 위한 폼 저감제 조성물

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1373903A (en) * 1972-12-11 1974-11-13 Dow Corning Carpet dyeing antifoam

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3235509A (en) * 1962-10-03 1966-02-15 Wacker Chemie Gmbh Method for producing antifoam agents
US3664961A (en) * 1970-03-31 1972-05-23 Procter & Gamble Enzyme detergent composition containing coagglomerated perborate bleaching agent
US4010110A (en) * 1971-08-06 1977-03-01 Drew Chemical Corporation Process for dispersing contaminants in circulating water or polar organic liquid system
BE788249A (fr) * 1972-05-15 1973-02-28 Dow Corning Compositions de silicones pour lutter contre le moussage dans les procedes de teinture au jet
GB1407997A (en) * 1972-08-01 1975-10-01 Procter & Gamble Controlled sudsing detergent compositions
GB1553610A (en) * 1975-10-14 1979-09-26 Procter & Gamble Non-liquid detergent compositions
US4075118A (en) * 1975-10-14 1978-02-21 The Procter & Gamble Company Liquid detergent compositions containing a self-emulsified silicone suds controlling agent
US4136045A (en) * 1976-10-12 1979-01-23 The Procter & Gamble Company Detergent compositions containing ethoxylated nonionic surfactants and silicone containing suds suppressing agents
US4199465A (en) * 1977-12-23 1980-04-22 The Procter & Gamble Company Laundry detergent substrate articles
DE2900063A1 (de) * 1979-01-02 1980-07-17 Henkel Kgaa Waschmittel mit einem gehalt an schaumdaempfend wirkendem polydimethylsiloxan und verfahren zu dessen herstellung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1373903A (en) * 1972-12-11 1974-11-13 Dow Corning Carpet dyeing antifoam

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7592296B2 (en) 2004-08-03 2009-09-22 Johnsondiversey, Inc. Conveyor track or container lubricant compositions

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ES8205426A1 (es) 1982-06-01
ES504304A0 (es) 1982-06-01
EP0046342A1 (en) 1982-02-24
US4400288A (en) 1983-08-23
MX153402A (es) 1986-10-07
GR75649B (el) 1984-08-02
DE3168893D1 (en) 1985-03-28

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